Two nickel coordination polymers with flexible ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene

The reaction of 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (ttmb) with Ni(II) salts yields two coordination polymers [Ni₃(ttmb)₂(H₂O)₆Cl₆](H₂O)₃ (1) and [Ni(ttmb)₂(H₂O)₂](NO₃)₂(H₂O)₄ (2). The flexible ligand ttmb shows the cis,cis,cis-conformation and a tri-monodentate coordination mode in 1. Each ttmb links three Ni(II) atoms to form an undulated (3, 4)-connected two-dimensional network. Each undulated two-dimensional network polycatenates other two identical networks, thus giving a rare (2D → 3D) parallel polycatenation network in 1. The ttmb ligand exhibits the cis,trans,trans-conformation and a two-monodentate coordination mode in 2. Each ttmb connects two Ni(II) atoms to construct a two-dimensional (4, 4) network in 2. The thermal stability of compounds 1 and 2 was studied.     

Syntheses,structures and photocatalytic properties of two coordination polymers based on bis(1,2,4-triazol-4-ylmethyl)benzene and multicarboxylates

Two coordination polymers {[Cu₄(OH)₂(btrb)₂(btc)₂]·4H₂O}_n (1) and {[Cd₂(btrb)(adc)₂(H₂O)]·H₂O}_n (2) were synthesized with hydrothermal method and characterized (btrb = 1,4-bis(1,2,4-triazol-4-ylmethyl)benzene, btc = 1,3,5-benzenetricarboxylate, adc = 1,3-adamantanedicarboxylate). 1 shows an unusual (3,10)-connected two-dimensional metal–organic framework based on the tetranuclear copper(II) cluster [Cu₄(μ₃-OH)₂]. 2 is an interesting three-dimensional network based on the one-dimensional metal–organic nanotube. 1 shows good photocatalytic activity for the degradation of methyl blue (MB). The luminescence of 2 was investigated.     

Counteranion-directed assembly of zinc(II) coordination polymers with 1,3,5-tris(1-imidazolyl)benzene

Two novel coordination polymers [Zn₂(tib)(chda)Cl₂] (1) and [Zn(tib)I]I (2) have been prepared by reactions of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2-cyclohexanedicarboxylic acid (H₂chda) with corresponding Zn(II) salts, respectively. Complex 1 has a three-dimensional (3D) structure with rare gra (graphite) topology, while 2 is a typical two-dimensional (2D) (4·8²) network. The results revealed that the counteranion plays a subtle and important role in the assembly procedure. Photoluminescent property of the complexes was investigated.     

Syntheses,structures and luminescence of zinc and cadmium coordination polymers with bis(1,2,4-triazol-1-yl)butane and benzenedicarboxylate

The self-assembly reactions of the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and rigid ligand 1,4-benzenedicarboxylate (bdc) with Zn(II) or Cd(II) give two novel coordination polymers {[Zn(bdc)(btb)](H₂O)₅}_n (1) and {[Cd₂(bdc)₂(btb)(H₂O)₂](H₂O)₇}_n (2). Coordination polymer 1, a supramolecular isomer of [Zn₂(bdc)₂(btb)₂](H₂O)₂ [X.L. Wang, C. Qin, E.B. Wang, Z.M. Su, Chem. Eur. J. 12 (2006) 2680], is a special 2D (6,3) network, with six Zn(II) atoms at six corners and four bdc and two double btb at six edges. Coordination polymer 2 exhibits a distorted 3D cubic topology that is built from dimer Cd₂ units. The blue luminescent emission maxima at 420 and 439 nm for 1, 440 and 455 nm for 2 were observed in the solid state at room temperature.     

A novel three-dimensional network silver coordination polymer with flexible bis(1,2,4-triazol-4-yl)ethane

The self-assembly reaction of the flexible ligand 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) and AgClO₄ gives a novel coordination polymer {[Ag(btre)](ClO₄)}_n (1). Adjacent two silver(I) atoms are linked through four nitrogen atoms of two N1/N2 atoms of two btre ligands and form Ag₂N₄ 6-membered rings and construct a one-dimensional chain. The chains extend through btre bridges in four different directions alternatively to construct a novel three-dimensional network. Compound 1 exhibits luminescence emission maxima at 326 nm upon excitation at 260 nm in the solid state at room temperature. The anion exchange of compound 1 with BF₄^? and NO₃^? occurs smoothly in a typical aqueous media.     

Temperature-controlled structural diversity of two Cd(II) coordination polymers based on a flexible tripodal multicarboxylate ligand

Two new 3-D Cd(II) coordination polymers (CPs) with 3,5-bi(4-carboxyphenoxy)-benzoic acid (H₃L), namely [Cd₃(L)₂(H₂O)₄]·4H₂O (1) and [Cd₃(L)₂(H₂O)₃]·2H₂O (2), were successfully synthesized under hydrothermal condition at 140 °C and 180 °C, respectively. Complex 1 is constructed from 1-D (–Cd–O–)_∞ rod-shaped SBUs (secondary building units) and ‘Y’-shaped L ligands. In complex 2, the 3-D network is mediated by 2-D [Cd(COO)₂]_n layered motifs and ‘T’ and ‘Y’-shaped L ligands. The results show that the reaction temperature plays a key role on the final structures of the complexes. The luminescent properties of the complexes have also been investigated.     

Electrochemical and spectral properties of meta-linked 1,3,5-tris(aryl)benzenes and 2,4,6-tris(aryl)-1-phenoles, and their polymers

We present electrochemical and spectral properties of symmetric monomers 1,3,5-tris(aryl)benzenes and 2,4,6-tris(aryl)-1-phenols and their polymers. These compounds contain thienyl, furyl or EDOT moieties attached to central benzene or phenol ring at the meta-position, synthesized by a Stille cross-coupling procedure. All monomers are electroactive and undergo electropolymerization creating thin films on an electrode surface. Polymers with meta-linkages were obtained by electrochemical oxidation. Detailed cyclic voltammetry and in situ UV-vis spectroelectrochemistry show that polymers with hydroxy groups exhibit higher conductivity and better stability than with benzene core. Interesting and different behavior occurs for 2,4,6-tris(2-thienyl)-1-phenol, for which the characteristic, sharp, redox peak is observed.     

实验筛选分离对氰基苄氯与1-(4-氰基苄基)-1H-1,2,4-三氮唑两种化合物的溶剂

为筛选分离对氰基苄氯和1-(4-氰基苄基)-1H-1,2,4-三氮唑较好的溶剂,采用静态平衡法测定了两种化合物在不同溶剂中的溶解度数据,为工业结晶分离工艺设计提供了基础数据.由分离系数的大小选出较好的溶剂,依次为乙酸乙酯、异丙醚和四氯化碳.采用λ-h方程对两种化合物在乙酸乙酯、异丙醚和四氯化碳溶剂中的溶解度数据进行了关...     

Crystal structure and photo-induced property of two-dimensional silver(I) complex with 1,3,5-tris(benzylsulfanyl)benzene

The silver(I) complex [Ag₂(3bsb)₂(ClO₄)₂] (1) (3bsb; 1,3,5-tris(benzylsulfanyl)benzene) has been prepared and its molecular structure was determined by X-ray crystallography. In 1, the silver ion prefers a tetrahedral coordination geometry and produces a two-dimensional sheet structure containing dimeric units. Irradiation of this complex 1 with light changes its color from white to pink; heat or exposure to acetone vapor makes the irradiated sample revert back to white. However, only 3bsb has no characteristic like this photochromism.     

Hydrothermal syntheses of two novel coordination polymers based on tetranuclear metal cluster constructed by 1,3,5-Tris(2H-tetrazol-5-yl)benzene ligand

Two new coordination polymers, namely [Zn₃(BTT)(μ₃-OH)₃] (1), and [Mn₃(BTT)(μ₃-OH)₃] (2), where H₃BTT = 1,3,5-Tris(2H-tetrazol-5-yl)benzene, have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction. The structure of compound 1 can be described as tetranuclear zinc cluster linked with zinc (Zn2^II) atoms to form a 2D layer, and the adjacent parallel layers bridged by the rigid H₃BTT ligand to show 3D network. Taking Mn ions in replace of Zn ions, a new compound 2 is successfully obtained which is isostructural with 1. In addition, photoluminescent property for 1, magnetic properties for 2 and thermogravimetric analyses for 1 and 2 are investigated in detail.     

Syntheses,structures and photocatalytic properties of three copper(II) coordination polymers

Three coordination polymers [Cu₂(obtz)₂(tdc)₂]_n (1), {[Cu(obtz)₂(H₂O)₂][Cu₂(obtz)₂(sip)₂]5.5H₂O}_n (2) and [Cu(obtz)(nip)]_n(3) were synthesized by the hydrothermal reaction (obtz = 1.2-bis(1,2,4-triazol-1-ylmethyl)benzene, tdc = 2.5-thiophenedicarboxylate, sip = 5-sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows a ladder-like one-dimensional chain with two side arms. 2 is comprised of two distinct and crystallographically independent polymeric motifs. The first motif in 2 is the ladder-like one-dimensional anionic chain with two side arms. The second motif in 2 is the cationic chain. 3 exhibits the intriguing 2-fold interpenetrated network based on the undulated 2D (4.4) network. 1, 2 and 3 are good photocatalysts for the degradation of methyl orange (MO) under UV irradiation.     

Syntheses,structures, and luminescent properties of zinc(II) complexes assembled with aromatic polycarboxylate and 1,3-bis(1,2,4-triazol-1-yl)propane

Three new coordination compounds, {[Zn(btrp)(ip)]?2H₂O}_n (1), {[Zn(btrp)(hip)]?2H₂O}_n (2), and {[Zn_1.5(btrp)(btc)(H₂O)]?H₂O}_n (3) (btrp = 1,3-bis(1,2,4-triazol-1-yl)propane, H₂ip = isophthalate, H₂hip = 5-hydroxy isophthalate, H₃btc = benzene-1,3,5-tricarboxylic acid) have been prepared via solvothermal method and characterized by single crystal X-ray diffraction and elemental analysis. 1 possesses 2D (4. 4) net framewok. 2 is also a 2D infinite layer framework, and the resulting 2D structure is interconnected by hydrogen-bond and π…π interactions to lead to a 3D supramolecular architecture. 3 exhibits a novel 2D framework with three nonequivalent points, {5.6²}{5².6}{5⁴.8²}. The fluorescence properties of 1–3 have been studied at room temperature.     

Syntheses,structures and luminescence of three copper(I) cyanide coordination polymers incorporating flexible N-donor ligands

Three copper(I) cyanide coordination polymers, namely [Cu₈(CN)₈(btmb)₂]_n (1), [Cu(CN)(btmb)_0.5]_n (2) and [Cu₂(CN)₂(dpa)]_n (3) (btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, dpa = di(4-pyridyl)amine), were synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectra, PXRD and thermogravimetric analyses. Single-crystal X-ray diffraction analyses reveal that complex 1 is an interesting 2D double-layered network constructing from eight distinct Cu(I) centers, eight μ₂-cyanides and two tetradentate cis-btmb ligands. Complex 2 is a ladder-like coordination polymer assembled by CuCN linear chain and bidentate trans-btmb linker. Complex 3 has a 2D wave-like network constructing from CuCN zigzag chain and V-shape dpa spacer. These coordination polymers are thermally stable up to 270–300 °C. They emit blue luminescence originating from ligand-centered emission.     

Syntheses,structures and photoluminescence properties of two 2D Cd(II) coordination polymers based on a semirigid tridentate N-donor ligand

The assembly of a semirigid tridentate N-donor ligand with Cd(II) ions afforded two novel coordination polymers, [Cd(tipa)(H₂O)₂·2NO₃·2DMF·H₂O]_n (1), [Cd₂(tipa)₂Cl₄·2DMF·6H₂O]_n (2), where tipa = tris(4-(1H-imidazol-1-yl)phenyl) amine. Structural analyses indicate that the two compounds feature 2D layered networks. A 3-connected uninodal net with point symbol of (8²·10) is constructed in compound 1 by the connection of tipa and metal ions, in which the terminally coordinated water molecules prevent further extension of the layer. Compound 2 features [Cd₂Cl₄] motifs, which are bridged by tridentate tipa ligands into a 2D (3,6)-connected layer. The results show that tipa with different dihedral angles between benzene ring and terminal imidazole groups can act as versatile building blocks for the generation of various networks. Moreover, the photoluminescence properties of 1 and 2 in the solid state at room temperature have been investigated.     

Three Cu(II) coordination polymers with novel bi-triazole ligand: Synthesis,structure and EPR properties

Three Cu(II) coordination polymers: [Cu(XL)(NO₃)₂]_n (1), {[Cu(XL)(4,4′-bpy)(NO₃)₂]·CH₃CN}_n (1a) and {[Cu(XL)₃](NO₃)₂·3.5H₂O}_n (2) have been synthesized mainly based on a novel bi-triazole ligand N,N′-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bi(1,2,4-triazole) (XL) and characterized by X-ray crystallography, EPR spectra, elemental analyses, FT-IR spectra and PXRD patterns. Structure analyses reveal that compounds 1 and 1a exhibit 1D chains, and compound 2 features a 2D cationic framework. Additionally, the Cu(II) ions with various coordination environment in compounds 1, 1a and 2 exhibit different EPR properties.     

Syntheses,structures and properties of three dumbbell-shape Cadmium (II) complexes constructed by a tripodal ligand via hydrogen-bonding assembly

Three hydrogen-bonding frameworks based on NH⋯N and NH⋯O Hbond linkages have been synthesized and structurally characterized by using ntb (tris(2-benzimidazoylmethyl)amine) to react with two Cd(II) salts in the presence of dysfunctional bridging spacers of NaN3, 4'4-bipy and H2tpa (terephthalic acid) respectively. The building blocks of three complexes exhibit dumbbell-shape which stacks each other in the lattice leading to three 3D hydrogen-bonding frameworks with diversiform topology net of distorted NaCl net, (4,4) layer and 4²⁴ · 6⁴ net.     

Two Cd(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses,structures and photocatalytic properties

Hydrothermal reactions of CdCl₂·2.5H₂O with 3,6-bis(imidazol-1-yl)carbazole (bmcz), 2-amine-1,4-benzenedicarboxylic acid (2-NH₂-1,4-H₂BDC) or 1,4-naphthalenedicarboxylic acid (1,4-H₂NDC) afforded two coordination polymers, [Cd(2-NH₂-1,4-BDC)(bmcz)]_n (1) and [Cd(1,4-NDC)(bmcz)]_n (2). Complexes 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 and 2 are isomorphic and exhibit 3D supermolecular structures. The solid state luminescent and optical properties of 1 and 2 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored.     

Syntheses,structures and properties of novel d10 coordination polymers based on 4-[(1H-imidazol-4-yl)methylamino]benzoic acid ligand

Complete and partial deprotonation of new ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H₂L) under hydrothermal conditions lead to the formation of two novel coordination polymers [ZnL]_n (1) and [Ag(HL)]_n (2). Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework with (4 · 6²)₂(4² · 6¹⁰ · 8³) topology, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions. Both 1 and 2 show remarkable thermal stability and complex 1 was found to show strong blue luminescence with emission maxima at 381 nm upon excitation at 347 nm in the solid state at room temperature.     

Syntheses,crystal structures,and magnetic studies of two cobalt(II) coordination polymers based on concurrent ligand extension

An ether bridged tetracarboxylic acid ligand, 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H₄L) was used to construct two Co(II) coordination polymers in presence of different nitrogen donor ligands such as 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp). The products formed under hydrothermal conditions are formulated as [Co₂L(4,4′-bpy)₂(H₂O)₃]_n (1) and {[Co(bpbp)₂(H₂L)]·H₂O}_n (2). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD) measurement. Compound 1 shows an intriguing (3,4,5)-connected 3D framework with a point symbol of (4² · 6² · 8²)(4² · 6⁵ · 8³)(6² · 8). Compound 2 is an unusual 3D supramolecular framework generated by the one-dimensional [Co(bpbp)(H₂L)]_n polymer chain. The magnetic properties of compounds 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.     

Syntheses and thermal properties of (sulfonylbisphenoxy)-containing cyclotriphosphazene polymers

A (sulfonylbisphenoxy)-containing cyclotriphosphazene polymer system has been prepared by polycondensation of (phenoxy)chlorocyclotriphosphazene and 4,4-sulfonylbisphenol. The syntheses by polycondensation using sodium salt of 4,4-sulfonylbisphenol and by interfacial polycondensation were carried out for comparison. The characterization, thermal stability, and fire resistance of the synthesized polymers were studied. Thermogravimetric analysis showed that the polymers prepared were stable to above 400°C in nitrogen and exhibited high char contents at elevated temperature. The result indicated that the presence of a sulfonyl group was helpful for enhancing thermal stability and the presence of a phosphphazene ring was the cause of the high char residue at elevated temperature.